EP0641029A2 - Element for a photovoltaic solar cell and process of fabrication as well as its arrangement in a solar cell - Google Patents

Element for a photovoltaic solar cell and process of fabrication as well as its arrangement in a solar cell Download PDF

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Publication number
EP0641029A2
EP0641029A2 EP94113324A EP94113324A EP0641029A2 EP 0641029 A2 EP0641029 A2 EP 0641029A2 EP 94113324 A EP94113324 A EP 94113324A EP 94113324 A EP94113324 A EP 94113324A EP 0641029 A2 EP0641029 A2 EP 0641029A2
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EP
European Patent Office
Prior art keywords
coating
electrode
solar cell
photovoltaic
doping
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP94113324A
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German (de)
French (fr)
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EP0641029A3 (en
Inventor
Helmut Dr. Hoegl
Ralf M. Kern
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Hoegl Helmut Dr
KERN, RALF M.
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TWIN SOLAR TECHNIK ENTWICKLUNG
Twin Solar-Technik Entwicklungs-GmbH
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Priority claimed from DE4328868A external-priority patent/DE4328868A1/en
Priority claimed from DE4336825A external-priority patent/DE4336825A1/en
Application filed by TWIN SOLAR TECHNIK ENTWICKLUNG, Twin Solar-Technik Entwicklungs-GmbH filed Critical TWIN SOLAR TECHNIK ENTWICKLUNG
Publication of EP0641029A2 publication Critical patent/EP0641029A2/en
Publication of EP0641029A3 publication Critical patent/EP0641029A3/en
Withdrawn legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035272—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
    • H01L31/035281—Shape of the body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/915—Electrolytic deposition of semiconductor

Definitions

  • the invention relates to an element of a photovoltaic solar cell with at least one elongated or rod or wire (or thread) or ribbon-shaped electrode, which has at least one photovoltaically effective coating on its surface, and to a method for its production and its arrangement in a photovoltaic Solar cell.
  • the object of the invention is to provide an element for photovoltaic solar cells which is improved in terms of its production costs and its efficiency, and a correspondingly improved solar cell.
  • the invention consists in that the electrode made of an electrically highly conductive material, in particular impure silicon with a multi- or polycrystalline, preferably monocrystalline structure, and the coating of a photovoltaically active material, in particular silicon with a, on the surface of the electrode certain doping (p- or n-doping).
  • both the current-conducting electrode and its coating are made of silicon, but with different structures, namely the electrode of impure, good current-conducting and the coating of the purest possible, but for the purpose Optimally effective photovoltaic effectiveness Doped silicon with a higher degree of purity.
  • a single coating of this kind on a silicon electrode would suffice in that the charge field (p- or n) formed in the coating forms the photovoltaic voltage field or the two opposite charge fields with the opposite charge carriers within the electrode, while the excess, i.e. Compared to the charge potential formed quantitatively in the coating, the freely movable charge carriers given in the electrode also serve the improved electrical conductivity of the Si electrode.
  • the edge region in the electrode can have a positive or negative charge field with a corresponding composition of the silicon and the coating can be doped accordingly in opposite directions (p- or n).
  • the electrode structure can be constructed in a multicrystalline manner, so that the coating can have a correspondingly coarse-crystalline, in particular also monocrystalline, structure due to its epitaxial effect.
  • the invention can be modified with the features of claims 2 and 3 and consists of a solar cell arrangement according to claims 4 to 11 and also includes the manufacturing method according to the other claims.
  • an elongated or shaped elongated, for example wire and ribbon-shaped electrode 2 is provided with a photovoltaically active coating 3 in longitudinal section and in cross section, which consists of a radially inner layer 5 and an outer layer attached thereon 6 can exist, the layers 5 and 6 being doped in opposite directions (p- or n).
  • an electrode 2 is shown analogously, but with only one coating 3 consisting of only a single layer of specific doping (p- or n - here p).
  • a charge field separation of electrons 12 (-) and - in the coating 3 - of "holes" (p) or + can form on both sides of the coating limit on the surface of the electrode, while an excess of electrons 13 serve to increase the electrical conductivity of the silicon can.
  • a doping layer 14 can also be shifted into the surface of the electrode 2, for example by the action of diffusion (or other effects) after prior diffusion cleaning or influencing just below the surface of the electrode material.
  • a photovoltaic solar cell is formed between electrodes 2 or as an arrangement of two electrodes 2 and counterelectrode 7, each with opposite doping of their coating surfaces, so that the current flows radially through the electrodes Coatings 3 flows between the electrodes 2 and 7.
  • two elements 1 with opposite doping on the surface of their coating 3 can be attached on a metallic surface (which may also be reflective) either at a distance of 8 or also connected to one another (analogously to FIGS. 5 and 6) in an electrically conductive manner.
  • the surface 9 as a photovoltaic element on the side facing the elements 1 can also be provided with a photovoltaically active coating 3 on which the elements 1 are attached in an electrically conductive manner.
  • the photovoltaically coated surface 10 acts as a counterelectrode, while the elements 1 are electrically conductively connected to the surface of the photovoltaic coating with a coating surface doped opposite to the surface of the photovoltaic coating at a lateral distance (8 analogous to FIG. 7).
  • Fig. 9 shows an application method by applying the coating material by continuous drawing e.g. an electrode wire 2 made of different materials such as metals (eg copper, aluminum, tungsten, V2A steel), on which in the direction 25 in front of the drawing dies 24 the coating material 27 is applied, which is also in front of each drawing die of the individual drawing stations 21-13 can jam.
  • an electrode wire 2 made of different materials such as metals (eg copper, aluminum, tungsten, V2A steel), on which in the direction 25 in front of the drawing dies 24 the coating material 27 is applied, which is also in front of each drawing die of the individual drawing stations 21-13 can jam.
  • the structure and the cross section of the electrode wire itself can also be influenced.
  • a controlled microstructure an optimally close and contamination-free connection of several layers to one another or on the surface of the electrode can be achieved with optimal uniformity and a thin layer thickness under the pressure conditions within the drawing nozzle.
  • the elongated wire, rod (or filament) or ribbon-shaped electrode can be coated most simply by means of liquid phase epitaxy (LPE), in which a particularly macro-crystalline, preferably very largely monocrystalline, silicon coating is formed in the following way:
  • LPE liquid phase epitaxy
  • silicon is also dissolved together with the required doping in liquid INDIUM or GALLIUM or bismuth or alloys, preferably saturated or supersaturated, of the surface to be coated into the melt under a reducing atmosphere, such as in hydrogen gas introduced in such a way that, when the temperature on the wire surface is reduced, the silicon is deposited in largely monocrystalline form together with the dopant in the desired doping concentration.
  • an AsIn melt is preferred as the solvent for the silicon including the dopant.
  • the temperature range used for crystal growth can be between 250 ° to 940 ° C, with a cooling rate of 5 ° to 16 ° C / h.
  • the crystal orientation of the substrate can be [100] or [111] or in other lengths.
  • Ga, GaGe or Ga-Si alloys are used as solvents for the deposition of gallium arsenide layers, the layer growth temperature range being 300 ° to 750 ° C with the same or similar cooling rate and the preferred substrate orientation [100] or [111].
  • the surface of the substrate can also initially be used chemically modified or doped by diffusion or converted into a first integrated photovoltaic layer (p or n) before - if necessary after cleaning the surface, for example in a drawing nozzle or a drawing or scraper - the silicon layers are applied in the above manner .
  • Profiled or textured surfaces can also be formed, for example wire or elongated profiles with longitudinal grooves.
  • a wire for example a silicon wire
  • a wire is cleaned on the surface (also, for example, by drawing in a drawing die or drawing profile or by means of etching) and then drawn through successively arranged deposition baths in which - with a choice of speed and exposure or immersion length - the silicon coating with - depending on the sequence of the deposition baths - optional layer thickness and sequence of the n and p layers.
  • the shaped wire coated in this way can then be solidified by drawing through a drawing die.
  • a particularly advantageous layer sequence lies in a silicon coating of a wire-shaped or elongated substrate (also made of C-fiber) that is chrome-plated or galvanized or cadmium-coated on its surface, and at the same time a radially inner rear-view mirroring of the photovoltaic layers with a correspondingly high degree of efficiency.
  • an elongated electrode serving as a carrier can also be chemically treated from the outside to its surface, so that the outer area of its cross section, depending on the material of the electrode, in the sense of a photovoltaically active edge area or its photovoltaic effect Edge area is converted.
  • Examples include zinc oxide for an electrode made of zinc, copper oxide (CuO) or copper oxide (CuO2) for an electrode made of copper, or also e.g. Magnesium oxide with an electrode made of magnesium.
  • the metallic electrode material can also be alloyed or structured in such a way that its chemical treatment results in a photovoltaically favorable mixed connection, possibly also at the same time with a doping effect.
  • the surface area can be one of those between the photovoltaic cells located on the circumference Material and the surface of the electrode provided thin SiO2 layer are converted to tunnel the electrons to the electrode.
  • all of the thread-like or elongate electrodes described are each provided with at least one photoactive p-doped and one surface-n-doped - or vice versa - or vice versa - they can also be provided in an identical arrangement, with all electrodes on their outer surface having the same charge polarity ( have p+ or e ⁇ ), and also side by side or with each other, also with each other on an electrically conductive support as a counter electrode, for example can be arranged as a surface and are thus directly in electrically conductive contact. All electrode wires form the one (+ or -) pole, to which the electrically conductive carrier for all electrode wires is the counter electrode. In this case, electrically conductive adhesive can be used for the contact connection of all electrode wires to one another and / or for fastening on the carrier surface.
  • the adhesive can also be applied in a line for the smallest possible thickness by means of the drawing process in a simultaneous, combined process, similar to and following that of FIG. 9.

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Abstract

The invention relates to an element of a photovoltaic solar cell having at least one elongated electrode which is in the form of a bar, wire (or filament) or strip, has at least one photovoltaically active coating on its surface, and is characterised in that the electrode consists of an electrically conductive material, especially impure silicon having polycrystalline, preferably monocrystalline structure, and the coating consists of a monocrystalline or polycrystalline photovoltaically active material, especially silicon having a defined doping (p-doping or n-doping), on the surface of the electrode, which material is, for example, continuously applied by means of a wire extrusion die.

Description

Die Erfindung betrifft ein Element einer photovoltaischen Solarzelle mit mindestens einer langgestreckten bzw. stab- oder draht (bzw. faden-) oder bandförmigen Elektrode, welche auf ihrer Oberfläche mindestens eine photovoltaisch wirksame Beschichtung aufweist sowie ein Verfahren zu seiner Herstellung sowie deren Anordnung in einer photovoltaischen Solarzelle.The invention relates to an element of a photovoltaic solar cell with at least one elongated or rod or wire (or thread) or ribbon-shaped electrode, which has at least one photovoltaically effective coating on its surface, and to a method for its production and its arrangement in a photovoltaic Solar cell.

Aufgabe der Erfindung ist es, eine bezüglich seiner Herstellungskosten und seines Wirkungsgrades verbessertes Element für photovoltaische Solarzellen sowie eine dementsprechend verbesserte Solarzelle zu schaffen.The object of the invention is to provide an element for photovoltaic solar cells which is improved in terms of its production costs and its efficiency, and a correspondingly improved solar cell.

Demgemäß besteht die Erfindung darin, daß die Elektrode aus einem elektrisch gut leitenden Material, insbesondere unreinem Silizium mit multi- oder polykristallinem, vorzugsweise monokristallinem Gefüge und die Beschichtung aus einem auf der Oberfläche der Elektrode mono- oder multikristallinem photovoltaisch wirksamen Material, insbesondere Silizium mit einer bestimmten Dotierung (p- oder n-Dotierung) besteht.Accordingly, the invention consists in that the electrode made of an electrically highly conductive material, in particular impure silicon with a multi- or polycrystalline, preferably monocrystalline structure, and the coating of a photovoltaically active material, in particular silicon with a, on the surface of the electrode certain doping (p- or n-doping).

In bevorzugter Ausführungsform besteht also sowohl die den Strom leitende Elektrode als auch deren Beschichtung aus Silizium, jedoch mit unterschiedlichem Aufbau, nämlich der Elektrode aus unreinem, gut Strom leitendem und der Beschichtung aus möglichst reinem, aber zwecks photovoltaisch optimaler Wirksamkeit gezielt dotiertem Silizium höheren Reinheitsgrades.In a preferred embodiment, both the current-conducting electrode and its coating are made of silicon, but with different structures, namely the electrode of impure, good current-conducting and the coating of the purest possible, but for the purpose Optimally effective photovoltaic effectiveness Doped silicon with a higher degree of purity.

Grundsätzlich würde eine einzige solche Beschichtung auf einer Siliziumelektrode ausreichen, indem das in der Beschichtung gebildete Ladungsfeld (p- oder n) mit den entgegengesetzten Ladungsträgern innerhalb der Elektrode das photovoltaische Spannungsfeld bzw. die zwei entgegengesetzten Ladungsfelder bildet, während die demgegenüber überschüssigen, d.h. gegenüber dem quantitativ in der Beschichtung gebildeten Ladungspotential zusätzlich in der Elektrode gegebenen frei beweglichen Ladungsträger der verbesserten elektrischen Leitfähigkeit der Si-Elektrode dienen.Basically, a single coating of this kind on a silicon electrode would suffice in that the charge field (p- or n) formed in the coating forms the photovoltaic voltage field or the two opposite charge fields with the opposite charge carriers within the electrode, while the excess, i.e. Compared to the charge potential formed quantitatively in the coating, the freely movable charge carriers given in the electrode also serve the improved electrical conductivity of the Si electrode.

Sinngemäß kann der Randbereich in der Elektrode bei entsprechender Zusammensetzung des Siliziums ein positives oder negatives Ladungsfeld aufweisen und die Beschichtung entsprechend entgegengesetzt (p- oder n) dotiert sein.Analogously, the edge region in the electrode can have a positive or negative charge field with a corresponding composition of the silicon and the coating can be doped accordingly in opposite directions (p- or n).

Bei der Verwendung von Silizium als Elektrodenmaterial kann das Elektrodengefüge multikristallin aufgebaut sein, so daß die Beschichtung aufgrund epitaktischer Wirkung entsprechend grob-kristallin, insbesondere auch monokristallin aufgebaut sein kann.When silicon is used as the electrode material, the electrode structure can be constructed in a multicrystalline manner, so that the coating can have a correspondingly coarse-crystalline, in particular also monocrystalline, structure due to its epitaxial effect.

Analoge Effekte können auch mit anderen Materialien zum Einsatz gebracht werden, auch z.B. Siliziumcarbid.Analogous effects can also be used with other materials, including silicon carbide.

Die Erfindung ist mit den Merkmalen der Patentansprüche 2 und 3 modifizierbar und besteht in einer Solarzellenanordnung gemäß den Patentansprüchen 4 bis 11 und umfaßt auch das Herstellungsverfahren gemäß den weiteren Patentansprüchen.The invention can be modified with the features of claims 2 and 3 and consists of a solar cell arrangement according to claims 4 to 11 and also includes the manufacturing method according to the other claims.

Die Erfindung ist nachstehend anhand von Figuren 1 bis 9 näher erläutert:
Gemäß Fig. 1 und 2 ist im Längsschnitt und im Querschnitt eine aus Silizium gezogene langgestreckte bzw. geformte langgestreckte, z.B. draht- und bandförmige Elektrode 2 mit einer photovoltaisch wirksamen Beschichtung 3 versehen, welche aus einer radial inneren Lage 5 und einer darauf angebrachten äußeren Lage 6 bestehen kann, wobei die Lagen 5 und 6 entgegengesetzt dotiert sind (p- bzw. n).The invention is explained in more detail below with reference to FIGS. 1 to 9:
1 and 2, an elongated or shaped elongated, for example wire and ribbon-shaped electrode 2 is provided with a photovoltaically active coating 3 in longitudinal section and in cross section, which consists of a radially inner layer 5 and an outer layer attached thereon 6 can exist, the layers 5 and 6 being doped in opposite directions (p- or n).

In den Fig. 3 und 4 ist analog eine Elektrode 2 jedoch mit nur einer Beschichtung 3 aus nur einer einzelnen Lage bestimmter Dotierung (p- oder n - hier p) dargestellt. Dabei kann sich beidseits der Beschichtungsgrenze auf der Oberfläche der Elektrode eine Ladungsfeldtrennung aus Elektronen 12 (-) und - in der Beschichtung 3 - aus "Löchern" (p) bzw. + bilden, während ein Elektronenüberschuß 13 einer Erhöhung der elektrischen Leitfähigkeit des Siliziums dienen kann.3 and 4, an electrode 2 is shown analogously, but with only one coating 3 consisting of only a single layer of specific doping (p- or n - here p). A charge field separation of electrons 12 (-) and - in the coating 3 - of "holes" (p) or + can form on both sides of the coating limit on the surface of the electrode, while an excess of electrons 13 serve to increase the electrical conductivity of the silicon can.

Auch kann z.B. durch Diffusionseinwirkung (oder andere Effekte) eine Dotierungsschicht 14 in die Oberfläche der Elektrode 2 hineinverlagert werden, insbesondere nach vorheriger Diffusionsreinigung bzw. Beeinflussung dicht unter der Oberfläche des Elektrodenmaterials.A doping layer 14 can also be shifted into the surface of the electrode 2, for example by the action of diffusion (or other effects) after prior diffusion cleaning or influencing just below the surface of the electrode material.

Beim Aneinanderfügen zweier Elemente aus beschichteten Elektroden 2 gemäß den Fig. 5 und 6 bildet sich zwischen den Elektroden 2 bzw. als Anordnung zweier jeweils als Elektrode 2 und Gegenelektrode 7 mit jeweils entgegengesetzter Dotierung ihrer Beschichtungsoberflächen eine photovoltaische Solarzelle, so daß der Strom radial durch die Beschichtungen 3 zwischen den Elektroden 2 und 7 fließt.5 and 6, a photovoltaic solar cell is formed between electrodes 2 or as an arrangement of two electrodes 2 and counterelectrode 7, each with opposite doping of their coating surfaces, so that the current flows radially through the electrodes Coatings 3 flows between the electrodes 2 and 7.

Gemäß Fig. 7 können jeweils zwei auf der Oberfläche ihrer Beschichtung 3 entgegengesetzt dotierte Elemente 1 auf einer metalischen Fläche (die auch reflektierend ausgeführt sein kann) entweder auf Abstand 8 oder auch aneinander (analog Fig. 5 und 6) elektrisch leitend verbunden angebracht sein.According to FIG. 7, two elements 1 with opposite doping on the surface of their coating 3 can be attached on a metallic surface (which may also be reflective) either at a distance of 8 or also connected to one another (analogously to FIGS. 5 and 6) in an electrically conductive manner.

Gemäß Fig. 8 kann die Fläche 9 als photovoltaisches Element auf der den Elementen 1 zugewandten Seite ebenfalls mit einer photovoltaisch wirksamen Beschichtung 3 versehen sein, auf der die Elemente 1 elektrisch leitend angebracht sind. Dabei wirkt die photovoltaisch beschichtete Fläche 10 als Gegenelektrode, während die Elemente 1 mit zur Oberfläche der photovoltaischenen Beschichtung entgegengesetzt dotierter Beschichtungsoberfläche auf lateralen Abstand (8 analog Fig. 7) auf der Oberfläche der photovoltaischen Beschichtung elektrisch leitend verbunden sind.8, the surface 9 as a photovoltaic element on the side facing the elements 1 can also be provided with a photovoltaically active coating 3 on which the elements 1 are attached in an electrically conductive manner. The photovoltaically coated surface 10 acts as a counterelectrode, while the elements 1 are electrically conductively connected to the surface of the photovoltaic coating with a coating surface doped opposite to the surface of the photovoltaic coating at a lateral distance (8 analogous to FIG. 7).

Fig. 9 zeigt ein Auftragungsverfahren mittels Aufbringung des Beschichtungsmaterials durch kontinuierliches Hindurchziehen z.B. eines Elektrodendrahtes 2 aus unterschiedlichen Materialien wie Metallen (z.B. Kupfer, Aluminium, Wolfram, V₂A-Stahl), auf dem in Laufrichtung 25 vor den Ziehsteinen 24 das Auftragen 26 des Beschichtungsmaterials 27 erfolgt, das sich auch vor jeder Ziehdüse der einzelnen Ziehstationen 21-13 stauen kann.Fig. 9 shows an application method by applying the coating material by continuous drawing e.g. an electrode wire 2 made of different materials such as metals (eg copper, aluminum, tungsten, V₂A steel), on which in the direction 25 in front of the drawing dies 24 the coating material 27 is applied, which is also in front of each drawing die of the individual drawing stations 21-13 can jam.

Mit diesem Verfahren kann auch das Gefüge und der Querschnitt des Elektrodendrahtes selbst beeinflußt werden. Jedenfalls läßt sich unter den Druckverhältnissen innerhalb der Ziehdüse eine gesteuerte Gefügeausbildung, eine optimal enge und verunreinigungsfreie Verbindung mehrerer Schichten miteinander bzw. auf der Oberfläche der Elektrode mit optimaler Gleichmäßigkeit und dünnschichtiger Schichtdicke erreichen.With this method, the structure and the cross section of the electrode wire itself can also be influenced. In any case, a controlled microstructure, an optimally close and contamination-free connection of several layers to one another or on the surface of the electrode can be achieved with optimal uniformity and a thin layer thickness under the pressure conditions within the drawing nozzle.

Unter den Druckverhältnissen innerhalb der Ziehdüse sind auch chemische Veränderungen (z.B. Oxidation bei Kupfer) der Elektrodenoberfläche oder der Auftragsmaterialien wie auch z.B. interkristalline Verbindungen möglich.Under the pressure conditions within the drawing nozzle there are also chemical changes (e.g. oxidation with copper) of the electrode surface or the application materials as well as e.g. intercrystalline compounds possible.

Die Beschichtung der langgestreckten draht-, stab- (bzw. faden-) oder bandförmigen Elektrode kann am einfachsten mittels liquid phase epitaxy (LPE) erfolgen, bei dem eine insbesondere makrokristalline, vorzugsweise sehr weitgehend monokristalline Siliziumbeschichtung auf folgende Weise gebildet wird:
Für p-Siliziumschichten wird Silizium auch gleich zusammen mit der benötigten Dotierung in flüssigem INDIUM oder GALLIUM oder auch Wismut oder Legierungen aus dieser gelöst, und zwar vorzugsweise gesättigt oder übersättigt, die zu beschichtende Oberfläche unter reduzierender Atmosphäre, wie z.B. in Wasserstoffgas, in die Schmelze derart eingebracht, daß bei Senkung der Temperatur an der Drahtoberfläche das Silizium in weitgehend monokristalliner Form mitsamt des Dotierungsmittels in gewünschter Dotierungskonzentration abgeschieden wird.The elongated wire, rod (or filament) or ribbon-shaped electrode can be coated most simply by means of liquid phase epitaxy (LPE), in which a particularly macro-crystalline, preferably very largely monocrystalline, silicon coating is formed in the following way:
For p-silicon layers, silicon is also dissolved together with the required doping in liquid INDIUM or GALLIUM or bismuth or alloys, preferably saturated or supersaturated, of the surface to be coated into the melt under a reducing atmosphere, such as in hydrogen gas introduced in such a way that, when the temperature on the wire surface is reduced, the silicon is deposited in largely monocrystalline form together with the dopant in the desired doping concentration.

Für eine Beschichtung in n-dotierter Form wird eine AsIn Schmelze als Lösungsmittel für das Silizium samt Dotierungsmittel bevorzugt.For a coating in n-doped form, an AsIn melt is preferred as the solvent for the silicon including the dopant.

Der für das Kristallwachstum verwendete Temperaturbereich kann zwischen 250° bis 940°C liegen, bei mit einer Abkühlungsrate von 5° bis 16° C/h. Die Kristallorientierung des Substrats kann bei [100] oder [111] oder in anderen Längen liegen.The temperature range used for crystal growth can be between 250 ° to 940 ° C, with a cooling rate of 5 ° to 16 ° C / h. The crystal orientation of the substrate can be [100] or [111] or in other lengths.

Für die Abscheidung von Gallium-Arsenide Schichten werden analog Ga, GaGe oder Ga-Si-Legierungen als Lösungsmittel eingesetzt, wobei der Schichtwachstums-Temperaturbereich bei 300° bis 750°C bei gleicher oder ähnlicher Abkühlungsgeschindigkeit liegt und die bevorzugte Substrat-Orientierung [100] oder [111]. Auf diese Weise können auch mehrere Schichten nacheinander übereinander auf die Drahtoberfläche aufgetragen werden. Auch kann erfindungsgemäß zunächst die Oberfläche des Substrats chemisch verändert oder diffusionsmäßig dotiert bzw. zu einer ersten integrierten photovoltaischen Schicht (p oder n) umgewandelt werden, bevor - ggf. nach Reinigung der Oberfläche z B. in einer Ziehdüse bzw. einem Zieh- odern Abstreifstein - die Siliziumschichten in vorstehender Weise aufgebracht werden.Analogously, Ga, GaGe or Ga-Si alloys are used as solvents for the deposition of gallium arsenide layers, the layer growth temperature range being 300 ° to 750 ° C with the same or similar cooling rate and the preferred substrate orientation [100] or [111]. In this way, several layers can be applied one after the other on the wire surface. According to the invention, the surface of the substrate can also initially be used chemically modified or doped by diffusion or converted into a first integrated photovoltaic layer (p or n) before - if necessary after cleaning the surface, for example in a drawing nozzle or a drawing or scraper - the silicon layers are applied in the above manner .

Auch können dabei profilierte bzw. texturierte Oberflächen gebildet werden, beispielsweise Draht- oder langgestreckte Profile mit längsverlaufenden Rillen.Profiled or textured surfaces can also be formed, for example wire or elongated profiles with longitudinal grooves.

Mit dem genannten Verfahren können z.B. Schichtdicken zwischen 0,5 µ und 100 µ abgeschieden werden. Verfahrensgemäß wird ein Draht, beispielsweise ein Siliziumdraht oberflächenmäßig gereinigt (auch z.B. durch Ziehen in einem Ziehstein bzw. Ziehprofil oder mittels Ätzen) und dann durch nacheinander geschaltete Abscheidebäder durchgezogen, in denen - bei wahlweiser Geschwindigkeit und Einwirkungs- bzw. Eintauchlänge - die Siliziumbeschichtung mit - je nach Folge der Abscheidebäder - wahlweiser Schichtdicke und Aufeinanderfolge der n- und der p-Schicht erfolgt. Der auf diese Weise beschichtete Formdraht kann anschließend mittels Ziehen durch einen Ziehstein gefügeverfestigt werden.With the method mentioned, e.g. Layer thicknesses between 0.5 µ and 100 µ can be deposited. According to the method, a wire, for example a silicon wire, is cleaned on the surface (also, for example, by drawing in a drawing die or drawing profile or by means of etching) and then drawn through successively arranged deposition baths in which - with a choice of speed and exposure or immersion length - the silicon coating with - depending on the sequence of the deposition baths - optional layer thickness and sequence of the n and p layers. The shaped wire coated in this way can then be solidified by drawing through a drawing die.

Eine besonders vorteilhafte Schichtfolge liegt in einer Siliziumbeschichtung eines auf seiner Oberfläche verchromten oder auch verzinkten oder cadmierten drahtförmigen bzw. langgestreckten Substrats (auch aus C-Faser), wobei zugleich eine radialinnere Hinterspiegelung der photovoltaischen Schichten mit entsprechend hohem Wirkungsgrad gegeben ist.A particularly advantageous layer sequence lies in a silicon coating of a wire-shaped or elongated substrate (also made of C-fiber) that is chrome-plated or galvanized or cadmium-coated on its surface, and at the same time a radially inner rear-view mirroring of the photovoltaic layers with a correspondingly high degree of efficiency.

Ähnliche photovoltaische Beschichtungen sind mit Molekularstrahl Epitaxy-Verfahren erzielbar.Similar photovoltaic coatings can be achieved using the molecular beam epitaxy process.

Analog zu der vorbeschriebenen Form und bevorzugten Ausführungsform kann zugleich eine als Träger dienende langgestreckte Elektrode von außen bis in ihre Oberfläche hinein chemisch behandelt sein, so daß der äußere Bereich ihres Querschnitts je nach Material der Elektrode im Sinne eines photovoltaisch wirksamen Randbereiches oder dessen photovoltaische Wirkung begünstigenden Randbereich umgewandelt wird.Analogous to the form and preferred embodiment described above, an elongated electrode serving as a carrier can also be chemically treated from the outside to its surface, so that the outer area of its cross section, depending on the material of the electrode, in the sense of a photovoltaically active edge area or its photovoltaic effect Edge area is converted.

Beispiele dafür sind Zinkoxid bei einer aus Zink bestehenden Elektrode, Kupferoxid (CuO) oder Kupferoxidul (CuO₂) bei einer aus Kupfer bestehenden Elektrode, oder auch z.B. Magnesiumoxid bei einer aus Magnesium bestehenden Elektrode.Examples include zinc oxide for an electrode made of zinc, copper oxide (CuO) or copper oxide (CuO₂) for an electrode made of copper, or also e.g. Magnesium oxide with an electrode made of magnesium.

Auch kann das metallische Elektrodenmaterial derart legiert oder gefügemäßig ausgebildet sein, daß dessen chemische Behandlung eine photovoltaisch günstige Mischverbindung ergibt, auch eventuell zugleich mit Dotierungseffekt.The metallic electrode material can also be alloyed or structured in such a way that its chemical treatment results in a photovoltaically favorable mixed connection, possibly also at the same time with a doping effect.

Bei Silizium als Elektrodenmaterial kann für den Fall einer Beschichtung mit z.B. Silizium nach Art der MIS-Zellen (Feldladungsstrang) der Oberflächenbereich zu einer der zwischen der auf dem Umfang befindlichen photovoltaischen Material und der Oberfläche der Elektrode vorgesehenen dünnen SiO₂-Schicht umgewandelt werden, um die Elektronen zur Elektrode zu tunneln.With silicon as the electrode material, in the case of a coating with, for example, silicon in the manner of the MIS cells (field charge strand), the surface area can be one of those between the photovoltaic cells located on the circumference Material and the surface of the electrode provided thin SiO₂ layer are converted to tunnel the electrons to the electrode.

Wenn sämtliche beschriebenen fadenförmigen bzw. langgestreckten Elektroden jeweils mit mindestens einer photoaktiven p-dotierten und einer darüber n-dotierten - oder umgekehrt - Oberflächenschicht versehen sind, können sie auch in identischer Anordnung vorgesehen sein, wobei alle Elektroden auf ihrer äußeren Oberfläche die gleiche Ladungspolarität (also p⁺ oder e⁻) aufweisen, und auch nebeneinander bzw. miteinander, auch aneinander auf einem elektrisch leitenden Träger als Gegenelektrode, z.B. als Fläche angeordnet sein können und damit unmittelbar in elektrisch leitenden Kontakt stehen. Dabei bilden jeweils alle Elektrodendrähte den einen (+ oder -) Pol, zu dem der elektrisch leitende Träger für alle Elektrodendrähte die Gegenelektrode ist. Dabei kann elektrisch leitender Klebstoff zur Kontaktverbindung aller Elektrodendrähte aneinander und/oder zur Befestigung auf der Trägeroberfläche verwendet werden.If all of the thread-like or elongate electrodes described are each provided with at least one photoactive p-doped and one surface-n-doped - or vice versa - or vice versa - they can also be provided in an identical arrangement, with all electrodes on their outer surface having the same charge polarity ( have p⁺ or e⁻), and also side by side or with each other, also with each other on an electrically conductive support as a counter electrode, for example can be arranged as a surface and are thus directly in electrically conductive contact. All electrode wires form the one (+ or -) pole, to which the electrically conductive carrier for all electrode wires is the counter electrode. In this case, electrically conductive adhesive can be used for the contact connection of all electrode wires to one another and / or for fastening on the carrier surface.

Auch die Aufbringung des Klebstoffs kann zwecks geringstmöglicher Dicke in einer Linie mittels des Ziehverfahrens in einem gleichzeitigen, kombinierten Verfahrenszug, ähnlich dem und folgend auf den der Fig. 9, erfolgen.The adhesive can also be applied in a line for the smallest possible thickness by means of the drawing process in a simultaneous, combined process, similar to and following that of FIG. 9.

Claims (21)

Element einer photovoltaischen Solarzelle mit mindestens einer langgestreckten bzw. stab- oder draht(bzw. faden-) oder bandförmigen Elektrode, welche auf ihrer Oberfläche mindestens eine photovoltaisch wirksame Beschichtung aufweist, dadurch gekennzeichnet, daß die Elektrode (2) aus einem elektrisch gut leitenden Material, insbesondere unreinem Silizium mit multikristallinem, vorzugsweise monokristallinem Gefüge und die Beschichtung (3) aus einem auf der Oberfläche (4) der Elektrode mono- oder multi- bzw. polykristalinen photovoltaisch wirksamen Material, insbesondere Silizium mit einer bestimmten Dotierung (p- oder n-Dotierung) besteht.Element of a photovoltaic solar cell with at least one elongated or rod or wire (or thread) or ribbon-shaped electrode which has at least one photovoltaically effective coating on its surface, characterized in that the electrode (2) is made of an electrically highly conductive material , in particular impure silicon with a multicrystalline, preferably monocrystalline structure and the coating (3) made of a material which is mono- or multi- or polycrystalline or photocrystalline on the surface (4) of the electrode, in particular silicon with a certain doping (p- or n- Doping). Element einer photovoltaischen Solarzelle nach Anspruch 1, dadurch gekennzeichnet, daß die Beschichtung (3) aus zwei koaxialen Lagen (5, 6) von entgegengesetzt dotiertem Material besteht.Element of a photovoltaic solar cell according to claim 1, characterized in that the coating (3) consists of two coaxial layers (5, 6) of oppositely doped material. Element einer photovoltaischen Solarzelle nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß mindestens die äußere photovoltaisch wirksame Lage (6) der Beschichtung (3) ein poly- bzw. mikrokristallines oder amorphes Gefüge aufweist.Element of a photovoltaic solar cell according to one of claims 1 or 2, characterized in that at least the outer photovoltaically effective layer (6) of the coating (3) has a polycrystalline or microcrystalline or amorphous structure. Solarzellenanordnung mit mindestens einem der Elemente nach den Ansprüchen 1 bis 3 und einer Gegenelektrode, dadurch gekennzeichnet, daß eine andere langgestreckte bzw. stab- oder draht- oder bandförmige Elektrode (7) als Gegenelektrode mit mindestens einer photovoltaisch wirksamen Beschichtung (3) mit auf ihrer Oberfläche entgegengesetzt zur Elektrode (2) gegebener Dotierung elektrisch leitend verbunden ist.Solar cell arrangement with at least one of the elements according to claims 1 to 3 and a counter electrode, characterized in that another Elongated or rod-shaped or wire-shaped or ribbon-shaped electrode (7) as the counter electrode with at least one photovoltaically active coating (3) with doping on its surface opposite to the electrode (2) is electrically conductively connected. Solarzellenanordnung nach Anspruch 4, dadurch gekennzeichnet, daß die auf ihrer Oberfläche n- oder p-beschichtete Elektrode (2) und die Gegenelektrode (7) mit ihren Oberflächen elektrisch leitend aneinander angeordnet sind bzw. in elektrisch leitendem Kontakt stehen.Solar cell arrangement according to claim 4, characterized in that the surface of the n- or p-coated electrode (2) and the counter electrode (7) are arranged in an electrically conductive manner with one another or are in electrically conductive contact. Solarzellenanordnung nach Anspruch 4, dadurch gekennzeichnet, daß Elektrode (2) und Gegenelektrode (7) parallel auf Abstand zueinander auf einer elektrisch leitenden Fläche (9) angeordnet und mit ihren Oberflächen über diese elektrisch leitend verbunden sind bzw. in Kontakt stehen.Solar cell arrangement according to Claim 4, characterized in that the electrode (2) and counterelectrode (7) are arranged in parallel at a distance from one another on an electrically conductive surface (9) and are electrically conductively connected or in contact with their surfaces via this. Solarzellenanordnung nach Anspruch 6, dadurch gekennzeichnet, daß eine flächige Gegenelektrode (7) mit mindestens einer photovoltaisch wirksamen Beschichtung (10) von zur Beschichtung (3) der Elektrode (2) entgegengesetzter Dotierung (p- oder n-) versehen ist, an deren Oberfläche die Beschichtung der Elektroden elektrisch leitend angebracht ist.Solar cell arrangement according to claim 6, characterized in that a flat counter electrode (7) is provided with at least one photovoltaically effective coating (10) of doping (p- or n-) opposite to the coating (3) of the electrode (2) , on the surface thereof the coating of the electrodes is attached in an electrically conductive manner. Solarzellenanordnung nach einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, daß als Verbindung der Oberflächen der Beschichtung (3) der Elektroden (2) mit der Gegenelektrode (7) ein elektrisch leitender Klebstoff verwendet ist.Solar cell arrangement according to one of claims 4 to 7, characterized in that as a connection of the surfaces of the coating (3) of the electrodes (2) with the counter electrode (7) is an electrically conductive adhesive. Solarzellenanordnung nach einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, daß die Oberfläche der Beschichtung (3) der Elektroden (2) und der Gegenelektroden (7) bzw. Gegenelektroden miteinander elektronenstrahl- oder laserverschweißt sind.Solar cell arrangement according to one of claims 4 to 7, characterized in that the surface of the coating (3) of the electrodes (2) and the counter electrodes (7) or counter electrodes are electron beam or laser welded together. Solarzellenanordnung nach einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, daß mindestens eine der photovoltaischen Schichten (3) in die Oberfläche der Elektrode (2) chemisch oder gefügemäßig eingearbeitet ist bzw. aus einer Umwandlung der Oberfläche der Elektrode (2) besteht.Solar cell arrangement according to one of claims 4 to 7, characterized in that at least one of the photovoltaic layers (3 ) is chemically or structurally incorporated into the surface of the electrode (2) or consists of a conversion of the surface of the electrode (2) . Solarzellenanordnung nach einem der vorhergehenden Ansprüche 6 und 7, dadurch gekennzeichnet, daß die Oberflächen der elektrisch leitenden Flächen (9) reflektierend bzw. verspiegelt ausgebildet sind.Solar cell arrangement according to one of the preceding claims 6 and 7, characterized in that the surfaces of the electrically conductive surfaces (9) are designed to be reflective or mirrored. Verfahren zur Herstellung eines Elements für eine photovoltaische Zelle nach einem der vorhergehenden Ansprüche 1 bis 11, dadurch gekennzeichnet, daß die insbesondere aus unreinem Silizium bestehende Elektrode nach ihrer Ausbildung zu langgestreckter bzw. stab- oder draht- (bzw. faden-) oder bandförmiger Form zur Bildung einer multi- oder polylkristallinen, vorzugsweise monokristallinen Beschichtung durch eine Schmelze aus n- oder p-dotiertem Beschichtungsmaterial, vorzugsweise reinem Silizium bewegt wird.Method for producing an element for a photovoltaic cell according to one of the preceding claims 1 to 11, characterized in that the electrode , which consists in particular of impure silicon, after its formation into an elongated or rod or wire (or thread) or ribbon-like shape is moved to form a multi- or poly-crystalline, preferably monocrystalline coating by a melt of n- or p-doped coating material, preferably pure silicon. Verfahren zur Herstellung eines Elements für eine photovoltaische Zelle nach einem der vorhergehenden Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Beschichtung mittels Elektronenstrahlverfahren, insbesondere ionengestütztem Elektronenstrahlverfahren, erfolgt (Dotierung n = Antimon oder Phosphor; Dotierung p = Gallium).Method for producing an element for a photovoltaic cell according to one of the preceding claims 1 to 12, characterized in that the coating is carried out by means of an electron beam method, in particular an ion-assisted electron beam method (doping n = antimony or phosphorus; doping p = gallium). Verfahren zur Herstellung eines Elements für eine photovoltaische Zelle nach einem der vorhergehenden Ansprüche 1 bis 13, dadurch gekennzeichnet, daß die Beschichtung elektrolytisch aufgetragen wird.Method for producing an element for a photovoltaic cell according to one of the preceding claims 1 to 13, characterized in that the coating is applied electrolytically. Verfahren zur Herstellung eines Elements für eine photovoltaische Zelle nach einem der vorhergehenden Ansprüche 1 bis 14, dadurch gekennzeichnet, daß die Beschichtung aus der Gasphase (z.B. Silan) erfolgt.Method for producing an element for a photovoltaic cell according to one of the preceding claims 1 to 14, characterized in that the coating is carried out from the gas phase (eg silane). Verfahren zur Herstellung eines Elements für eine photovoltaische Zelle nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Beschichtung elektrophoretisch aufgetragen wird.Method for producing an element for a photovoltaic cell according to one of the preceding claims, characterized in that the coating is applied electrophoretically. Verfahren zur Herstellung eines Elements für eine photovoltaische Zelle nach einem der vorhergehenden Ansprüche 1 bis 10, dadurch gekennzeichnet, daß das Material der Oberfläche der Elektrode chemisch umgewandelt wird.Method for producing an element for a photovoltaic cell according to one of the preceding claims 1 to 10, characterized in that the material of the surface of the electrode is chemically converted. Verfahren zur Herstellung eines Elements für eine photovoltaische Zelle nach einem der vorhergehenden Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Beschichtung mittels Auftragen des photovoltaischen Materials wie z.B. Sputtern, Besprühen, Laserbeschichten, elektrostatisch Beschichten, Elektrodenstrahlbeschichten, Aufdampfen oder Aufsintern erfolgt und das aufgetragene Material mittels Ziehen durch Ziehdüsen bzw. Ziehsteine auf oder in die Oberfläche des Materials der Elektrode auf- bzw. eingearbeitet wird.Method for producing an element for a photovoltaic cell according to one of the preceding claims 1 to 10, characterized in that the coating is carried out by applying the photovoltaic material such as sputtering, spraying, laser coating, electrostatic coating, electrode beam coating, vapor deposition or sintering and the applied material by pulling through drawing nozzles or drawing dies on or into the surface of the material of the electrode. Verfahren nach Anspruch 17, dadurch gekennzeichnet, daß die Beschichtung in mehreren Auftrag- und Ziehstationen im kontinuierlichen Durchzug angebracht wird.A method according to claim 17, characterized in that the coating is applied in several application and drawing stations in a continuous pass. Verfahren nach Anspruch 17 und/oder 18, dadurch gekennzeichnet, daß mehrere photovoltaische Schichten nacheinander aufgetragen werden.A method according to claim 17 and / or 18, characterized in that several photovoltaic layers are applied in succession. Verfahren nach einem der Ansprüche 11 bis 20, dadurch gekennzeichnet, daß der Auftrag der Beschichtung unter gleichzeitiger Anwendung von Mikrowellen erfolgt.Method according to one of claims 11 to 20, characterized in that the coating is applied with the simultaneous use of microwaves.
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